Mechanism of the Mukaiyama aldol reaction: The first solid-state characterization of a trichlorotitanium aldolate

Article abstract of DOI:10.1021/om00017a087

The reaction of the silyl ketene acetal Me₂C=C(OMe)OSiMe₃ (1) with preformed TiCl₄carbonyl adducts (the monomeric [PhC(O)C(O)PhTiCl₄] (2) and the dimeric {[MesCHOTi(Cl)₃]₂(μ-Cl)₂} (Mes = 2,4,6-Me₃C₆H₂; 3)) led to the isolation and structural characterization of the corresponding titanium aldolate complexes {[(PhCO)PhC(O)C(Me₂)C(OMe)OTi(Cl)₂] ₂(μ-Cl)₂} (4) and {[MesCH(O)C(Me₂)C(OMe)OTi(Cl)₂]₂(μ-Cl) ₂} (5), in which the aldolate fragment functions as a bidentate ligand in dimeric titanium complexes bridged by two chlorine atoms. Crystallographic details: 4 is monoclinic, space group P2₁/n, with a = 9.029(1) A?, b = 17.468(2) A?, c = 13.165(2) A?, β = 98.81(2)°, Z = 2, and R = 0.53.